US4968621A - Method for the wet degreasing of hide and skin stock - Google Patents
Method for the wet degreasing of hide and skin stock Download PDFInfo
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- US4968621A US4968621A US07/391,638 US39163889A US4968621A US 4968621 A US4968621 A US 4968621A US 39163889 A US39163889 A US 39163889A US 4968621 A US4968621 A US 4968621A
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- bating
- degreasing
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
Definitions
- the present invention relates to a method for the wet degreasing of hides and skins, and particularly of raw hides, skins, pelts, and wet blues, in the course of leather processing.
- the natural fat to be removed is deposited mostly at the boundary between the papillary and reticular layers and also in the subcutaneous connective tissue, and more particularly in the interior of fat cells which are embedded in collagenous connective tissue. Whether this embedded natural fat can be removed depends, among other things, on whether the membranes of the fat cells can be rendered sufficiently permeable or whether they can be destroyed, and on whether the collagenous enveloping tissue can be sufficiently loosened. [See F. Stather, Gerschenemie und Gerbereitechnologie ("Tanning Chemistry and Tanning Technology”), Akademie-Verlag, Berlin, 1967.]
- Fat dissolving emulsifiers have long been used to degrease hides and skins. The treatment frequently proceeds with aqueous solutions which contain emulsified fat solvents. (See F. Stather, loc. cit., p. 208.) A wide variety of emulsifying and wetting agents, and particularly fatty alkyl sulfates and soaps, are used as emulsifiers, while gasoline or chlorinated hydrocarbons are used as emulsified fat solvents. According to U.S. Pat. No. 2,343,929, an emulsion of trichloroethylene, water, and sulfonated oleyl alcohol, for example, is suitable for the degreasing of hides and skins.
- German patent No. 913,094 proposes the concurrent use of chlorinated hydrocarbons and the products of saponification of sulfochlorinated saturated hydrocarbons having a chain length of C 12 to C 24 as emulsifiers.
- German patent No. 759,631 which points out that the tendency of alkylsulfonic salts to proteolysis is a drawback.
- lipases too, are often used to degrease skins. (See Chem. Abstr. 97, 57467; 89, 199097c; 90, 205804v; 82, 74484a.) According to Chem. Abstr. 88, 171809, the lipolytic activity of an enzyme is considerably reduced by the surface active agent used. According to Chem. Abstr. 82, 113205g, none of the usual methods (ultrasonics, lipase action, or solvent extraction) will remove more than 50 percent of the fat in pigskins. It is pointed out that enzymatic lipolysis with lipase must be closely controlled since the enzyme is capable of decomposing collagen.
- enzymatic lipolysis is employed, it is effected by means of lipases and/or enzyme preparations containing lipase, in keeping with the chemical nature of the substrates, usually in the pH range below 8, and preferably in a moderately acid pH range.
- the object of the invention is the degreasing of hides, skins, pelts and wet blues which contain more than 2 weight percent of natural fat, based on the weight of the stock.
- This category includes, in particular, cattle hides of certain origins, for example the United States and Queensland, English ox hides, and Scandinavian hides, as well as pigskins of practically any provenance, sheepskins, lambskins, pickled skins, (especially those from New Zealand), and goatskins. Because of the modern trend toward the use of fattening feeds, the natural fat content of hides and skins of practically any origin has increased considerably over the last decade. Today it often exceeds tolerable levels and gives rise to the difficulties in leather manufacture mentioned earlier.
- the object of the invention is accomplished by a method wherein an enzymatic bating of skin stock with proteolytic enzymes is carried out in the presence of synthetic surface active substances.
- Suitable synthetic surface- active substances are, for example, the commonly used emulsifying agents, and particularly those suited for the emulsification of fat in water. (See British patent No. 586,540, German patent No. 894,142, and French patents Nos. 899,983 and 918,523.)
- Nonionic emulsifiers of the following types are primarily suitable for use in the method of the invention:
- Anionic emulsifiers of the following types are also suitable for use:
- cationic emulsifiers for example, those of the types:
- the emulsifiers suitable for use in accordance with the invention have hydrophile-lipophile balance (HLB) (oil in water emulsion) ranging from 8 to 18, more particularly from 9 to 15, and preferably from 12 to 15. (See Ullmanns Enzyklopadie der ischen Chemie, 4th ed., vol. 10.) Combinations of emulsifiers, and particularly of nonionic and anionic emulsifiers, may also be used to advantage.
- HLB hydrophile-lipophile balance
- Ethoxylated alkylphenols (alkylphenol polyglycols) with a degree of ethoxylation (ethylene oxide units) ranging from 4 to 40, and preferably with 6.5 moles ethylene oxide and/or with 12 ethylene oxide units per nonylphenol, are particularly suitable, optionally combined with anionic emulsifiers.
- the proteases which are used in the wet degreasing process under bating conditions in accordance with the invention should be selected with due regard to the pH conditions of the bating process.
- alkaline proteases here are proteases which are active (usually against casein) in the alkaline pH range (pH 8 and up).
- these are the pancreatic proteases, the alkaline bacterial proteases (EC 3.3.21.14), and the alkaline fungal proteases, for example.
- Particularly well suited for use are the proteases obtained from bacillus species such as B. subtilis, B. alcalophilus, B. licheniformis, B. coreus, and B. mycoides, and especially the so-called subtilisins.
- the neutral proteases which are active (against casein or hemoglobin) in the pH range from 6 to 9.
- neutral bacterial proteases EC 3.4.24.4.
- neutral fungal proteases for example, aspergilli such as A. oryzae.
- acid proteases for example those of animal origin such as pepsin and trypsin, plant proteases such as papain, and proteases of microbiological origin such as the fungal proteases, and particularly those from aspergilli, and more particularly from A. saitoi, A. oryzae, and A. niger, from penicillia such as P. roqueforte, from Rhiz.
- chinensis or from Mucor pusillus.
- Their activity is in the range from pH 2 to pH 7. It has been found that the degreasing process of the invention is carried out to great advantage as part of the bating process described in U.S. Pat. No. 4,273,876, in other words by the concurrent use of proteases and amylases during acid bating.
- the amount of the enzymes in the enzymatic mixture will generally range from 0.01 to 0.2 weight percent, based on the weight of the hide stock, for enzyme products with from 300 to 10,000 and preferably from 1,000 to 5,000 Lohlein-Volhard units/gram, the amount depending on the activity of the enzymes used.
- mineral oils containing from 45 to 50 weight percent of aromatic hydrocarbons e.g. "Gravex Oil 917", a product of Shell
- auxiliary substances such as hydrotropes, for example urea, and/or of cumene sulfonate has proved helpful. These should be used in amounts ranging from 0.01 mole to 1 mole/liter, and preferably from 0.02 to 0.2 mol/liter.
- Salted raw hides are preferably subjected to a cleansing soak in a drum, paddle vat, or mixer with about 1 to about 400 percent of water at 25° to 28° C. for about 2 hours.
- a small amount of surfactants (from 0.2 to 0.5 percent, based on the salted weight) may be added even to this bath. However, the amounts of fat so emulsified usually are minor.
- proteases with optimum activity in the pH range from 9 to 11. Their use results in better leather qualities than can be obtained in other pH ranges.
- One or more synthetic surfactants is added to the bath preferably at the same time as the enzyme.
- the surfactant should be added in an amount ranging from 0.1 to 5 weight percent, and more particularly from 0.2 to 1.5 weight percent, and preferably in an amount of 0.5 ⁇ 0.2 weight percent, based on the weight of the hide stock.
- the soaking treatment should be carried out for 4 to 6 hours.
- samples should be taken from the bath before soaking is ended and analyzed for fat content, preferably by the Seesand method and with dichloromethane as fat solvent in conformity with DIN 53,345, Part 7.
- Deliming and bating then follow, the latter as the process of the invention.
- Deliming and bating are best carried out as one continuous operation in the drum.
- the bath should contain about 50 weight percent of water at about 30° C.
- acid salts such as ammonium sulfate or sodium bisulfite, or a commercial deliming agent, are added in an amount ranging from 1 to 3 weight percent and the bath is agitated for about 30 minutes.
- acid salts such as ammonium sulfate or sodium bisulfite, or a commercial deliming agent
- Bating in accordance with the invention then follows. From about 50 to 70 percent of water, preferably at 30° C., is added to the deliming bath, following which proteolytic enzymes, selected from those listed above, are added in the form of a bate. If desired, mineral oil containing from 45 to 50 weight percent of aromatic hydrocarbons may be added, either simultaneously or subsequently.
- enzymatic bate having a proteolytic activity from 500 to 10,000 Lohlein-Volhard units per gram of bate should be used.
- the amount used depends, among other things, on the origin of the raw stock from which the leather is to be made.
- the synthetic surfactants or the emulsifiers are added along with the bate and the bath is agitated.
- the amount of the synthetic surfactants used may range from 0.05 to 5 weight percent, more particularly from 0.1 to 1.5 weight percent, and preferably ranges from 0.3 to 0.5 weight percent.
- the degreasing action will be enhanced by the above addition of a mineral oil containing from 45 to 50 weight percent of aromatic hydrocarbons, for example "Gravex Oil 917".
- the average bating time is about 1 hours at 30° C. At the end of that time, samples should be taken to determine the fat content. This determination can be made in conformity with DIN 53,345, Part 7.
- the liquor in the case of cattle hides normally has a fat content from 1 to 1 5.grams/liter.
- the liquor is found to have a fat content from 2 to 3 g/l.
- the method of the invention can be carried out to advantage as an acid bating operation.
- Acid bating may also be employed without a bating operation carried out in the neutral or slightly alkaline pH range. While bating performed in the neutral or alkaline pH range produces an opening up, cleansing, and degreasing of the grain, bating carried out in the acid pH range results in an opening up and degreasing of the flesh side. The two processes thus supplement each other. In carrying them out, the skin is first drummed for 20 minutes with an approximately 5 percent solution of common salt.
- acid bates containing proteases having optimum activity in the acid pH range are added. They usually have an enzymatic activity from 30 to 60 U Hb (Anson units) and are used in an amount ranging from 0.5 to 5 weight percent, based on the weight of the skins
- the optimum pH of the bate enzymes is advantageously established by the addition of 0.2 to 0.5 percent of formic acid (85% technical), based on the weight of the skins, diluted with water in the ratio of 1:10.
- the bath is generally agitated for about 90 minutes at about 30° C.
- the entire treatment is carried out overnight, the bath being agitated every three hours for about 3 minutes at 30° C.
- the liquor is discarded.
- degreasing is carried out in a fresh bath with synthetic surfactants, preferably a combination of emulsifiers. Of the latter, 2 weight percent are added to the bath, which is then agitated for about 2 hours.
- the emulsifiable amount of fat will be from about 20 to 25 percent greater than when degreasing is carried out with a combination of emulsifiers alone.
- the emulsifier combination preferably used for this purpose is composed of an ethoxylated alkylphenol and of an alkali metal sulfonate or ammonium alkylbenzene sulfonate in a ratio of 2:1, for example.
- Wet blues can also be treated and wet degreased by the acid bating process described.
- HBL hydrophile-lipophile balance
- the proteolytic activity of enzymes is best determined by the Lohlein-Volhard method ["Die Lohlein-Volhard'sche Methode Kunststoff Beêt der proteolytician Aktivitat ("The Lohlein-Volhard Method for Determination of Proteolytic Activity"), Gerbereitechnisches Taschenbuch, Dresden-Leipzig, 1955] and is expressed in Lohlein-Volhard units (LVU).
- Lohlein-Volhard method Die Lohlein-Volhard'sche Methode Kunststoff Beêt der proteolytician Aktivitat
- Aktivitat The Lohlein-Volhard Method for Determination of Proteolytic Activity
- Gerbereitechnisches Taschenbuch, Dresden-Leipzig, 1955 is expressed in Lohlein-Volhard units (LVU).
- LVU Lohlein-Volhard units
- U Hb proteinase units
- alkylphenol with 12 EO means a C 8 -C 9 alkylphenol ethoxylated with 12 ethylene oxide units.
- the sodium alkylbenzene sulfonate used is the product "MARLON A 350" of Huls having from 10 to 14 carbon atoms in the alkyl group.
- the acid bate used is one based on fungal proteases from A. parasiticus or A. oryzae, for example the "EROPIC” products of Rohm GmbH.
- the alkaline enzymatic bate used is a combination of pancreatic trypsin and a protease derived from B. subtilis, for example the product "OROPON OR" of Rohm GmbH.
- the mineral oil employed has a content of aromatic hydrocarbons between 45 and 50 percent by weight.
- the amount of fat emulsifiable with degreasing agents is found to be 23.8% greater.
- the skins are first divided into left and right halves. In the various operations, the left halves are worked without the addition of degreasing agents and the right halves with degreasing agents.
- Comparative soaking tests are run with 100 kg each of dried sheepskins.
- test (a) soaking is carried out solely with water with an inlet temperature of 30° C. The next morning, samples are taken and the fat content of the liquor is determined by the Seesand method.
- test (b) 1 gram of an enzymatic softener from Bacillus subtilis having 1,750 LVU/g per liter of liquor is added under the same condition. The next morning, a sample is taken as in test (a) and its fat content is determined.
- test (c) there is used, in addition to the substance of test (b), a surfactant mixture composed of 0.35 g of alkylphenol with 12 EO and 0.15 g of sodium alkylbenzene sulfonate per liter of liquor. The next morning, a sample is taken from the soaking liquor and analyzed for its fat content.
- test (d) soaking and wet degreasing are carried out with the addition of 0.35 g/l of alkylphenol with 12 EO and 0.15 g/g of sodium alkylbenzene sulfonate. Agitation, treating time and sampling as in test (a).
- the fat content of the liquor from the treatment with a surfactant mixture in test (d), namely 1.67 g/l, is taken as 100%, then the fat content of 1.94 g/l of liquor obtained in test (c) with a combination of enzymes and surfactant mixture represents 116.2%.
- the fat content of the liquor from test (c) (wet degreasing with a surfactant mixture), namely 8.54 g/l, is taken as 100%
- the increased fat content obtained in test (d) by combining said surfactant mixture with an enzymatic bate represents 159.2%.
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Abstract
A method for the wet degreasing of raw hides and skins, pelts, and wet blues under the conditions of enzymatic bating, wherein enzymatic bating of the hide stock is carried out with proteolytic enzymes in the presence of synthetic surface active substances, for example, a mixture of a non-ionic emulsifier and anionic emulsifier.
Description
This is a continuation of Ser. No. 088,467 filed Aug. 19, 1987 and now abandoned, which is a continuation of application Ser. No. 594,711, filed Mar. 29, 1984 and now abandoned.
The present invention relates to a method for the wet degreasing of hides and skins, and particularly of raw hides, skins, pelts, and wet blues, in the course of leather processing.
While in the case of calfskins, cattle hides, and goatskins the normal content of natural fat usually is less than 1 weight percent based on the dry weight of the hide stock and as a rule is reduced still further in the subsequent beamhouse operations so that generally no difficulties are encountered in tanning and finishing, this is not the case with skins that are higher in natural fat, and especially with sheepskins. Even after they have been put through the beamhouse, such hides and skins have a high residual fat content which, in the tanning that follows, results in the nonuniform takeup of tanning agents by the hide or skin, and consequently in grease stains, nonuniform dyeing, and finishing difficulties.
In the hides and skins which are higher in fat content (for example, sheepskins, goatskins, and cattle hides), the natural fat to be removed is deposited mostly at the boundary between the papillary and reticular layers and also in the subcutaneous connective tissue, and more particularly in the interior of fat cells which are embedded in collagenous connective tissue. Whether this embedded natural fat can be removed depends, among other things, on whether the membranes of the fat cells can be rendered sufficiently permeable or whether they can be destroyed, and on whether the collagenous enveloping tissue can be sufficiently loosened. [See F. Stather, Gerbereichemie und Gerbereitechnologie ("Tanning Chemistry and Tanning Technology"), Akademie-Verlag, Berlin, 1967.]
Fat dissolving emulsifiers have long been used to degrease hides and skins. The treatment frequently proceeds with aqueous solutions which contain emulsified fat solvents. (See F. Stather, loc. cit., p. 208.) A wide variety of emulsifying and wetting agents, and particularly fatty alkyl sulfates and soaps, are used as emulsifiers, while gasoline or chlorinated hydrocarbons are used as emulsified fat solvents. According to U.S. Pat. No. 2,343,929, an emulsion of trichloroethylene, water, and sulfonated oleyl alcohol, for example, is suitable for the degreasing of hides and skins.
German patent No. 913,094 proposes the concurrent use of chlorinated hydrocarbons and the products of saponification of sulfochlorinated saturated hydrocarbons having a chain length of C12 to C24 as emulsifiers.
The concurrent use of various types of emulsifiers is recommended in German patent No. 759,631, which points out that the tendency of alkylsulfonic salts to proteolysis is a drawback.
In the prior art, lipases, too, are often used to degrease skins. (See Chem. Abstr. 97, 57467; 89, 199097c; 90, 205804v; 82, 74484a.) According to Chem. Abstr. 88, 171809, the lipolytic activity of an enzyme is considerably reduced by the surface active agent used. According to Chem. Abstr. 82, 113205g, none of the usual methods (ultrasonics, lipase action, or solvent extraction) will remove more than 50 percent of the fat in pigskins. It is pointed out that enzymatic lipolysis with lipase must be closely controlled since the enzyme is capable of decomposing collagen. Where enzymatic lipolysis is employed, it is effected by means of lipases and/or enzyme preparations containing lipase, in keeping with the chemical nature of the substrates, usually in the pH range below 8, and preferably in a moderately acid pH range.
The detrimental effect with emulsifiers, particularly ionic emulsifiers, and other surface active agents have on enzymes is widely documented.
The wet degreasing of hides and skins, pelts and wet blues is increasingly beset by problems, including antipollution regulations. For example, there are serious objections from the viewpoint of ecology, safety, and/or industrial hygiene to the use of halogenated hydrocarbons and certain more volatile fat solvents in the degreasing of hides and the like.
Since, as a rule, reduction of natural fat content to about 2 percent, based on the dry weight of the hides, will satisfy the technical requirements concerning further processability and, ultimately, the quality of the leather produced, the object of the invention is the degreasing of hides, skins, pelts and wet blues which contain more than 2 weight percent of natural fat, based on the weight of the stock. This category includes, in particular, cattle hides of certain origins, for example the United States and Queensland, English ox hides, and Scandinavian hides, as well as pigskins of practically any provenance, sheepskins, lambskins, pickled skins, (especially those from New Zealand), and goatskins. Because of the modern trend toward the use of fattening feeds, the natural fat content of hides and skins of practically any origin has increased considerably over the last decade. Today it often exceeds tolerable levels and gives rise to the difficulties in leather manufacture mentioned earlier.
These difficulties are compounded by the fact that the fat deposits are not uniformly distributed over the surface of the hide; rather, there are high fat and low fat zones. In places with pronounced natural fat deposits, diffusion of the commonly used chemicals and auxiliary agents is rendered more difficult and often a uniform effect over the entire cross section of the hides and skins is not obtained. The severity of these problems increases with the thickness of the hide or skin.
Accumulations of fat result in insufficient softening action and, consequently, in insufficient opening of the hide structure in liming. Areas of the hide which have not been sufficiently opened up in liming cannot be tanned through and result in uneven distribution of the tanning material over the cross section of the hide. Nonuniform penetration of the tanning material in turn results in nonuniform reaction in the subsequent operations, such as neutralization, retannage, dyeing, and fatliquoring. Higher natural fat contents of the grain layer always result in nonuniform dyeing, which is detrimental especially to full grained, aniline dyed leathers. Higher natural fat contents also reduce the adhesive strength of the finish and further result in poorer physical properties, such as poorer tear resistance.
In carrying out the object of the invention, it should be possible substantially to adhere to the existing and proven technology, both in the beamhouse and in the subsequent steps of tanning, retannage, fatliquoring, dyeing, etc.
The object of the invention is accomplished by a method wherein an enzymatic bating of skin stock with proteolytic enzymes is carried out in the presence of synthetic surface active substances.
Suitable synthetic surface- active substances are, for example, the commonly used emulsifying agents, and particularly those suited for the emulsification of fat in water. (See British patent No. 586,540, German patent No. 894,142, and French patents Nos. 899,983 and 918,523.) Nonionic emulsifiers of the following types, for example, are primarily suitable for use in the method of the invention:
(A) Polyglycol derivatives
(a) Fatty acid polyglycols,
(b) Fatty alcohol polyglycol ethers,
(c) Alkylphenol polyglycol ethers, and
(d) Fatty acid ethanolamide polyglycol ethers.
(B) Glycerol derivatives
(a) Fatty acid monoglycerides, and
(b) Fatty acid polyglycerol esters.
Anionic emulsifiers of the following types, for example, are also suitable for use:
(C) Sulfates R--OSO3 Na
(a) Fatty alkyl sulfates, both primary, and secondary,
(b) Ethoxylated fatty alkyl sulfates,
(c) Monoglyceride sulfates, and
(d) Products of sulfation of unsaturated oils and fatty acids.
(D) Sulfonates R SO3 Na
(a) Alkylbenzene sulfonates,
(b) Alkyl sulfonate,
(c) Fatty acid condensation products,
(d) Petroleum sulfonates
(e) Products of sulfitation of unsaturated fatty oils and fatty acids,
(f) Short chain alkylbenzene sulfonates, e.g. of cumene, toluene or xylenol.
Less advantageous are cationic emulsifiers, for example, those of the types:
(E) Amine salts RNR, R2 Hx ##STR1## (a) Ammonium salts, (b) Pyridinium salts, wherein R is a long chain alkyl group having from 8 to 24 carbon atoms and R1, R2 and R3 are short chain alkyl groups having up to 6 carbon atoms.
The emulsifiers suitable for use in accordance with the invention have hydrophile-lipophile balance (HLB) (oil in water emulsion) ranging from 8 to 18, more particularly from 9 to 15, and preferably from 12 to 15. (See Ullmanns Enzyklopadie der technischen Chemie, 4th ed., vol. 10.) Combinations of emulsifiers, and particularly of nonionic and anionic emulsifiers, may also be used to advantage. Ethoxylated alkylphenols (alkylphenol polyglycols) with a degree of ethoxylation (ethylene oxide units) ranging from 4 to 40, and preferably with 6.5 moles ethylene oxide and/or with 12 ethylene oxide units per nonylphenol, are particularly suitable, optionally combined with anionic emulsifiers.
The concurrent use of proteolytic enzymes in some steps of the beamhouse operations is known per se. An enzymatic bating process is known from German patent No. 974,813 in which enzymes derived from microorganisms, and plant, animal, mineral, or synthetic oils act on the skins either simultaneously or successively. According to German patent No. 1,120,066, enzyme preparations may be used in bating with the addition of optionally emulsified oils.
The proteases which are used in the wet degreasing process under bating conditions in accordance with the invention should be selected with due regard to the pH conditions of the bating process. Thus, both alkaline to neutral and acid proteases may be used. Alkaline proteases here are proteases which are active (usually against casein) in the alkaline pH range (pH 8 and up). Among these are the pancreatic proteases, the alkaline bacterial proteases (EC 3.3.21.14), and the alkaline fungal proteases, for example. Particularly well suited for use are the proteases obtained from bacillus species such as B. subtilis, B. alcalophilus, B. licheniformis, B. coreus, and B. mycoides, and especially the so-called subtilisins.
Of interest are, moreover, the neutral proteases, which are active (against casein or hemoglobin) in the pH range from 6 to 9. These include neutral bacterial proteases (EC 3.4.24.4.) and neutral fungal proteases, for example, aspergilli such as A. oryzae. Also of interest are the acid proteases, for example those of animal origin such as pepsin and trypsin, plant proteases such as papain, and proteases of microbiological origin such as the fungal proteases, and particularly those from aspergilli, and more particularly from A. saitoi, A. oryzae, and A. niger, from penicillia such as P. roqueforte, from Rhiz. chinensis or from Mucor pusillus. Their activity (against hemoglobin) is in the range from pH 2 to pH 7. It has been found that the degreasing process of the invention is carried out to great advantage as part of the bating process described in U.S. Pat. No. 4,273,876, in other words by the concurrent use of proteases and amylases during acid bating.
The amount of the enzymes in the enzymatic mixture will generally range from 0.01 to 0.2 weight percent, based on the weight of the hide stock, for enzyme products with from 300 to 10,000 and preferably from 1,000 to 5,000 Lohlein-Volhard units/gram, the amount depending on the activity of the enzymes used. In a particularly preferred embodiment, mineral oils containing from 45 to 50 weight percent of aromatic hydrocarbons (e.g. "Gravex Oil 917", a product of Shell) may also be simultaneously added to the degreasing mixture in an amount ranging from 0.1 to 5.0 weight percent, based on the weight of the hide stock.
Moreover, the addition of auxiliary substances such as hydrotropes, for example urea, and/or of cumene sulfonate has proved helpful. These should be used in amounts ranging from 0.01 mole to 1 mole/liter, and preferably from 0.02 to 0.2 mol/liter.
The facts set forth in outlining the object of the invention make it clear why degreasing is best carried out in several steps in different beamhouse operations. It has been found that the soaking and bating operations are particularly well adapted to wet degreasing. Surprisingly, the concurrent use of proteolytic enzymes and synthetic surface active substances (emulsifying agents), optionally in the presence of fat solvents, produces a synergistic effect several times greater than the effect of the individual components (enzymes and emulsifiers).
On the other hand, past experience indicates that in the liming operation no appreciable improvement in wet degreasing is obtained when synthetic surractants are used in the usual concentrations.
In the process of the invention, the following procedure may be employed:
(a) Salted raw hides are preferably subjected to a cleansing soak in a drum, paddle vat, or mixer with about 1 to about 400 percent of water at 25° to 28° C. for about 2 hours.
A small amount of surfactants (from 0.2 to 0.5 percent, based on the salted weight) may be added even to this bath. However, the amounts of fat so emulsified usually are minor.
(b) After the liquor has been replaced, soaking is started. Soaking is likewise carried out with about 1 to about 400 percent of water (guide value) and at 26° to 28° C. Proteolytic enzymes of the types indicated are added to the soak liquor (generally from 0.1 to 1 weight percent, based on the salted weight, of an enzyme having an activity of from 1,000 to 5,000 Lohlein-Volhard units per gram of enzyme).
Particularly preferred are proteases with optimum activity in the pH range from 9 to 11. Their use results in better leather qualities than can be obtained in other pH ranges.
One or more synthetic surfactants (emulsifiers) is added to the bath preferably at the same time as the enzyme. As a rule, the surfactant should be added in an amount ranging from 0.1 to 5 weight percent, and more particularly from 0.2 to 1.5 weight percent, and preferably in an amount of 0.5±0.2 weight percent, based on the weight of the hide stock.
The soaking treatment should be carried out for 4 to 6 hours.
For determination of the degreasing effect, samples should be taken from the bath before soaking is ended and analyzed for fat content, preferably by the Seesand method and with dichloromethane as fat solvent in conformity with DIN 53,345, Part 7.
As a result of the steps preceding the process in accordance with the invention, it will be observed at the conclusion of the soaking operation that in the case of cattle hides or pigskins as much as 30 weight percent of the total extractable natural fat has been removed. Liming is then carried out in the usual way. This is followed by the mechanical operations of fleshing and, in the case of cattle hides, of splitting.
Deliming and bating then follow, the latter as the process of the invention. Deliming and bating are best carried out as one continuous operation in the drum. At the start, the bath should contain about 50 weight percent of water at about 30° C. Then acid salts such as ammonium sulfate or sodium bisulfite, or a commercial deliming agent, are added in an amount ranging from 1 to 3 weight percent and the bath is agitated for about 30 minutes. When these conditions are observed, a section through the skin will show that it is largely free of lime at the end of that time. (Test with phenolphthalein solution.)
Bating in accordance with the invention then follows. From about 50 to 70 percent of water, preferably at 30° C., is added to the deliming bath, following which proteolytic enzymes, selected from those listed above, are added in the form of a bate. If desired, mineral oil containing from 45 to 50 weight percent of aromatic hydrocarbons may be added, either simultaneously or subsequently.
Based on the weight of the hide or skin stock or on the pelt weight, from 0.01 to 3 percent of enzymatic bate having a proteolytic activity from 500 to 10,000 Lohlein-Volhard units per gram of bate should be used. The amount used depends, among other things, on the origin of the raw stock from which the leather is to be made. The synthetic surfactants or the emulsifiers are added along with the bate and the bath is agitated.
The amount of the synthetic surfactants used may range from 0.05 to 5 weight percent, more particularly from 0.1 to 1.5 weight percent, and preferably ranges from 0.3 to 0.5 weight percent. The degreasing action will be enhanced by the above addition of a mineral oil containing from 45 to 50 weight percent of aromatic hydrocarbons, for example "Gravex Oil 917". The average bating time is about 1 hours at 30° C. At the end of that time, samples should be taken to determine the fat content. This determination can be made in conformity with DIN 53,345, Part 7.
In the prior art bating process, the liquor in the case of cattle hides normally has a fat content from 1 to 1 5.grams/liter. When the process of the invention is used, the liquor is found to have a fat content from 2 to 3 g/l.
The method of the invention can be carried out to advantage as an acid bating operation.
With many crude stock varieties<for example pigskins, sheepskins, goatskins, pickled pelts, splits, and wet blues, improvement of the leather quality seems to require that acid bating be carried out in addition to alkaline bating. Acid bating may also be employed without a bating operation carried out in the neutral or slightly alkaline pH range. While bating performed in the neutral or alkaline pH range produces an opening up, cleansing, and degreasing of the grain, bating carried out in the acid pH range results in an opening up and degreasing of the flesh side. The two processes thus supplement each other. In carrying them out, the skin is first drummed for 20 minutes with an approximately 5 percent solution of common salt. Then acid bates containing proteases having optimum activity in the acid pH range (pH 4 to 6) are added. They usually have an enzymatic activity from 30 to 60 UHb (Anson units) and are used in an amount ranging from 0.5 to 5 weight percent, based on the weight of the skins The optimum pH of the bate enzymes is advantageously established by the addition of 0.2 to 0.5 percent of formic acid (85% technical), based on the weight of the skins, diluted with water in the ratio of 1:10. At the start, the bath is generally agitated for about 90 minutes at about 30° C. The entire treatment is carried out overnight, the bath being agitated every three hours for about 3 minutes at 30° C.
At the end of the treating time, the liquor is discarded. After an intermediate wash, degreasing is carried out in a fresh bath with synthetic surfactants, preferably a combination of emulsifiers. Of the latter, 2 weight percent are added to the bath, which is then agitated for about 2 hours. After acid bating, the emulsifiable amount of fat will be from about 20 to 25 percent greater than when degreasing is carried out with a combination of emulsifiers alone.
The emulsifier combination preferably used for this purpose is composed of an ethoxylated alkylphenol and of an alkali metal sulfonate or ammonium alkylbenzene sulfonate in a ratio of 2:1, for example.
Wet blues can also be treated and wet degreased by the acid bating process described.
With regard to hydrophile-lipophile balance (HBL), reference is made to Rompps Chemi-Lexikon, 7th ed., Franckh'sche Verlagsbuchhandlung, Stuttgart, 1973.
The proteolytic activity of enzymes is best determined by the Lohlein-Volhard method ["Die Lohlein-Volhard'sche Methode zur Bestimmung der proteolytischen Aktivitat ("The Lohlein-Volhard Method for Determination of Proteolytic Activity"), Gerbereitechnisches Taschenbuch, Dresden-Leipzig, 1955] and is expressed in Lohlein-Volhard units (LVU). One LVU is the amount of enzyme which under the specific conditions of the method will digest 1.725 mg of casein.
So far as determination of the activity of enzymes active in the acid pH range, based on the Anson method [M. L. Anson, J. Gen Physiol. 22, 79 (1939))], is concerned, the units are known as "proteinase units (hemoglobin)", or UHb. One UHb is the amount of enzyme that will catalyst the liberation of fragments soluble in trichloroacetic acid from hemoglobin at a rate equivalent to 1 mole of tyrosine per minute at 37° C. (measured 280 nm). 1 mUHb =10-3 UHb.
In the examples which follow, "alkylphenol with 12 EO" means a C8 -C9 alkylphenol ethoxylated with 12 ethylene oxide units.
The sodium alkylbenzene sulfonate used is the product "MARLON A 350" of Huls having from 10 to 14 carbon atoms in the alkyl group.
The acid bate used is one based on fungal proteases from A. parasiticus or A. oryzae, for example the "EROPIC" products of Rohm GmbH.
The alkaline enzymatic bate used is a combination of pancreatic trypsin and a protease derived from B. subtilis, for example the product "OROPON OR" of Rohm GmbH.
The mineral oil employed has a content of aromatic hydrocarbons between 45 and 50 percent by weight.
______________________________________
Comparative degreasing of pickled skivers before and after
acid bating
______________________________________
Starting material: 8 New Zealand skivers.
The skivers are divided into left and right halves.
Pickled weight:
Left halves - 3.2 kg
Right halves - 3.8 kg.
Degreasing of left halves before acid bating:
Depickling
80.0% water, 30° C.
(drum):
5.0% common salt
Agitate for 20 minutes.
1.5% sodium bicarbonate
Agitate for 30 minutes.
Specific gravity, 9.5° Be; pH 6.5
1.32% nonylphenol with 12 EO
0.68% sodium alkylbenzene sulfonate
Agitate for 2 hours.
Sampling of liquor for fat analysis. Found 8.37 g/half =
23.6%. (Fat of hides extractable with dichloromethane before
degreasing = 100%).
Degreasing of right halves after acid bating:
Depickling
80.0% water, 30° C.
(drum):
5.0% common salt
Agitate for 20 minutes.
1.5% sodium bicarbonate
Agitate for 30 minutes.
Specific gravity, 9.5° Be; pH 6.4
Drain liquor.
Enzymatic loosening (drum):
100.0% water, 30° C.
1.5% acid bate with 30 mU.sub.Hb (Anson units)
(520) from A. oryzae
Agitate 90 minutes.
Treating time: Overnight
Agitate every hour for 3 minutes.
Washing: 200.0% water, 30° C.
Agitate for 20 minutes.
Discard liquor.
Degreasing:
80.0% water, 30° C.
1.32% alkylphenol with 12 EO
0.68% sodium alkylbenzene sulfonate
Agitate for 2 hours.
Sampling of liquor for fat analysis. Found 16.83
g/half = 47.4%. (Fat of hides extractable with
dichloromethane before degreasing = 100%).
______________________________________
Thus, after acid bating, the amount of fat emulsifiable with degreasing agents is found to be 23.8% greater.
Starting material: 10 U.S. pigskins, salted.
Salted weight: 55 kg.
The skins are first divided into left and right halves. In the various operations, the left halves are worked without the addition of degreasing agents and the right halves with degreasing agents.
______________________________________
Cleansing soak
250.0% water, 30° C.
(drum):
0.18% nonylphenol with 6.5 EO
0.18% mineral oil
0.02% nonylphenol with 4.0 EO
0.07% petroleum
0.05% ammonium cumene sulfonate
Agitate for 1 hour.
Take samples for fat
analyses.
Discard liquor.
Main soak 200.0% water, 30° C.
(drum):
0.5% enzymatic protease from B.
licheniformis having
4,000 LVU
0.5% soda ash
1.0% caustic soda sol., 33%
0.09% nonylphenol with 6.5 O
0.09% mineral oil
0.01% nonylphenol with 4.0 EO
0.035% petroleum
0.025% ammonium cumene sulfonate
Agitate for 2 hours.
Take samples for fat
analysis.
Discard liquor.
Liming (drum):
50.0% water, 30° C.
1.5% lime
1.5% sulfide-free liming aid
2.0% sulfide lime
1.0% caustic soda sol., 33%
0.10% nonylphenol with 6.5 EO
0.10% mineral oil
0.02% nonylphenol with 4.0 EO
0.07% petroleum
0.05% ammonium cumene sulfonate
Agitate for 1 hour.
2.5% lime
1.0% caustic soda solution, 33%
70.0% water, 25° C.
Overnight, agitate for 5
minutes every hour.
Take sample of lime liquor
for fat analysis.
Discard liquor.
Washing (drum):
200.0% water, 28° C.
Agitate for 20 minutes.
Discard liquor.
Repeat washing operation
once.
Deliming (drum):
50.0% water, 28° C.
2.0% ammonium sulfate
0.6% sodium bisulfite
Agitate for 30 minutes.
Bating (drum):
Add 100.0% water, 37° C.
1.0% enzymatic bate with trypsin
and protease from B. subtilis
having 300 LVU
0.18% nonylphenol with 6.5 EO
0.18% mineral oil
0.02% nonylphenol with 4.0 EO
0.07% petroleum
0.05% ammonium cumene sulfonate
Agitate for 2 hours.
Take sample for fat analysis.
Discard liquor.
Washing (drum):
200.0% water, 26° C.
Agitate for 20 minutes.
Discard liquor.
Acid bating:
100.0% water, 25° C.
8.0% common salt
1.5% acid enzymatic bate with
30 mU.sub.Hb after Anson
from A. parasiticus
Add 0.5% formic acid 85%, diluted 1:10
Agitate for 90 minutes.
0.66% alkylphenol with 10 moles EO
0.34% sodium alkylbenzene sulfonate
Agitate for 1 hour.
Take sample for fat analysis.
Pickling (drum):
Add 1.0% sulfuric acid, conc., diluted
1:10
Agitate for 1 hour.
Overnight, agitate for 5
minutes every hour.
Take sample of pickling
liquor for fat analysis.
Tanning (drum):
Add 10.0% "Chromosal B" (a basic
chromium (III) sulfate)
undissolved.
Agitate for 2 hours.
Basifying (drum):
Add 1.0% sodium bicarbonate, 1:20,
dissolved over 1 hour.
Keep drumming for 5 hours.
Final pH of tanning liquor,
3.8.
______________________________________
______________________________________
Fat analyses
Fat, grams/liter Left halves
Right halves
______________________________________
Cleansing soak 3.15 7.44
Main soak 25.36 24.86
Liming 12.17 15.31
Bating 2.99 8.66
Acid bating 2.00 8.75
Pickling 3.29 9.23
After tanning 1.27 7.64
50.23 g/l 81.89 g/l
100% 163%
Fat content of wet blue
10.1 4.4% based
on dry
weight
______________________________________
______________________________________
Comparative degreasing tests on unsplit Canadian bull pelts
in bating
______________________________________
Pelt weight:
500 kg each for the left and right bull
halves. The left halves were treated with
degreasing agents, the right halves without
degreasing agents.
Deliming (drum):
50.0% water, 30° C.
3.5% ammonium sulfate
0.5% bisulfite
Agitate for 30 minutes.
Bating (drum):
Add 70.0% water, 30° C.
0.6% bate with 1,500 LVU of a
combination of pancreatic trypsin
and a protease derived from B.
subtilis
0.2% alkylphenol with 12 EO
0.1% sodium alkylbenzene sulfonate
Agitate for 1 hour.
______________________________________
Take samples of bating liquors for fat analysis. Drain bating liquor. Fat content of bating liquor without degreasing agent, 1.6 g/l. Fat content of bating liquor with degreasing agent, 2.4 g/l.
By combining proteolytic enzymes in the bate with fat dissolving emulsifiers, a 50% increase in degreasing action was obtained. The finished leathers made from the material treated with a degreasing agent had greater fullness and a softer hand.
______________________________________
Process for the wet degreasing of hide and skin stock
______________________________________
Starting material:
1 wet blue hide from a Canadian
bullhide.
Shaved thickness:
1.8 mm
Shaved weight:
15.0 kg
Washing (drum):
200.0% water, 40° C.
0.5% acetic acid
Agitate 45 minutes.
Drain liquor.
Neutralization
150.0% water, 40° C.
(drum) 1.0% sodium formate
Agitate for 10 minutes.
Add 0.7% sodium bicarbonate dissolved
1:10
Agitate for 30 minutes, pH
5.5.
Drain liquor.
Divide into four quarters
Test 4 (a) (drum):
150.0% water, 50° C.
Agitate for 3 hours.
Fat content of liquor, 0.12
g/l.
Test 4 (b) (drum):
150.0% water, 50° C.
0.35% alkylphenol with 12 EO
0.15% sodium alkylbenzene sulfonate
Agitate for 3 hours.
Fat content of liquor, 1.4
g/l.
Test 4 (c) (drum):
150.0% water, 50° C.
1.5% acid bate with 30 mU.sub.Hb after
Anson from Aspergillus oryzae
Agitate for 3 hours.
Fat content of liquor, 0.4 g/l
Test 4 (d) (drum):
150.0% water, 50° C.
1.5% acid bate with 30 mU.sub.Hb after
Anson from A. oryzae.
0.35% alkylphenol with 12 EO
0.15% sodium alkylbenzene sulfonate
Agitate for 3 hours.
Fat content of liquor, 2.0
g/l.
______________________________________
If the fat content of the liquor from test 4(b), namely 1.4 g/l is taken as 100%, then combining the acid bate of test 4(c) with the degreasing agent of test 4(b) results in a fat content of the liquor from test 4(d) of 2.0 g/l, or 142.8%.
Comparative soaking tests are run with 100 kg each of dried sheepskins. In test (a), soaking is carried out solely with water with an inlet temperature of 30° C. The next morning, samples are taken and the fat content of the liquor is determined by the Seesand method. In test (b), 1 gram of an enzymatic softener from Bacillus subtilis having 1,750 LVU/g per liter of liquor is added under the same condition. The next morning, a sample is taken as in test (a) and its fat content is determined. In test (c), there is used, in addition to the substance of test (b), a surfactant mixture composed of 0.35 g of alkylphenol with 12 EO and 0.15 g of sodium alkylbenzene sulfonate per liter of liquor. The next morning, a sample is taken from the soaking liquor and analyzed for its fat content.
In test (d), soaking and wet degreasing are carried out with the addition of 0.35 g/l of alkylphenol with 12 EO and 0.15 g/g of sodium alkylbenzene sulfonate. Agitation, treating time and sampling as in test (a).
______________________________________
Test (a):
Raw stock:
100 kg (dry weight) of dried German sheepskins.
Soaking (drum):
800 1 water, 28° C.
At the start, agitate for 30 minutes.
Allow to stand for 1 hour.
Agitate for 2 minutes at 90 minute
intervals.
The next morning, take a sample of the
liquor for fat analysis.
Fat content of liquor: 0.4 g/l
Test (b):
Raw stock:
100 kg (dry weight of dried German sheepskins.
Soaking (drum):
800 1 water, 28° C.
Wet degreasing:
1 g enzymatic softening aid from Bacillus
subtilis with 1,750 LVU/g per liter of
liquor.
Agitation, treating time and sampling
as in test (a).
Fat content of liquor: 0.7 g/l.
Test (c):
Raw stock:
100 kg (dry weight) of dried German sheepskins
Soaking (drum):
800 1 water, 28° C.
1 g enzymatic softening aid from Bacillus
subtilis with 1,750 LVU/g per liter
of liquor
0.35 g/l alkylphenol with 12 EO
0.15 g/l sodium alkylbenzene sulfonate
Agitation, treating time and
sampling as in test (a).
Fat content of liquor: 1.94 g/l
Test (d):
Raw stock:
100 kg (dry weight) of dried German sheepskins
Soaking (drum):
800 1 water, 28° C.
0.35 g/l alkylphenol with 12 EO
0.15 g/l sodium alkylbenzene sulfonate
Agitation, treating time and
sampling as in test (a).
Fat content of liquor: 1.67 g/l
______________________________________
If the fat content of the liquor from the treatment with a surfactant mixture in test (d), namely 1.67 g/l, is taken as 100%, then the fat content of 1.94 g/l of liquor obtained in test (c) with a combination of enzymes and surfactant mixture represents 116.2%.
Divide each of two pelts into 4 quarters to give 8 quarters (Percentages based on pelt stock)
______________________________________
Test (a):
Wet degreasing (drum):
50.0% water, 27° C.
8.0% sodium chloride
1.5% ammonium sulfate
Agitate for 2 hours, pH 5.5.
Fat content of liquor: 0.44
g/l.
Test (b):
Wet degreasing (drum):
50.0% water, 27° C.
8.0% sodium chloride
1.5% ammonium sulfate
1.5% enzymatic bate from A. oryzae
with 30 mU.sub.Hb after Anson
Agitate for 2 hours, pH 5.5.
Fat content of liquor: 0.60
g/l.
Test (c):
Wet degreasing (drum):
50.0% water, 27° C.
8.0% sodium chloride
1.5% ammonium sulfate
1.35% alkylphenol with 12 EO
0.15% sodium alkylbenzene sulfonate
Agitate for 2 hours, pH 5.5.
Fat content of liquor: 8.54
g/l.
Test (d):
Wet degreasing (drum):
50.0% water, 27° C.
8.0% sodium chloride
1.5% ammonium sulfate
1.5% enzymatic bate from A. oryzae
with 30 mU.sub.Hb after Anson
0.35% alkylphenol with 12 EO
0.15% sodium alkylbenzene sulfonate
Agitate for 2 hours, pH 5.5.
Fat content of liquor: 13.6
g/l.
______________________________________
If the fat content of the liquor from test (c) (wet degreasing with a surfactant mixture), namely 8.54 g/l, is taken as 100%, the increased fat content obtained in test (d) by combining said surfactant mixture with an enzymatic bate represents 159.2%.
Claims (14)
1. A method for the wet degreasing of hide stock consisting of raw hides or skins, pelts, or wet blues under the conditions of enzymatic bating, which method involves enzymatically bating said hide stock with a bate consisting essentially of deliming agents, a proteolytic enzyme, and a combination of synthetic surface active substances including a nonionic emulsifier together with an anionic emulsifier.
2. A method as in claim 1 wherein said enzymatic bating is carried out in an acid pH range.
3. A method as in claim 1 wherein said emulsifiers have an HLB value, with respect to their oil-in-water emulsifying activity, from 8 to 18.
4. A method as in claim 3 wherein said HLB value is from 9 to 15.
5. A method as in claim 1 wherein said combination of synthetic surface active substances is present in an amount from 0.1 to 5 percent, by weight of the hide stock.
6. A method as in claim 1 wherein said combination of synthetic surface active substances is present in an amount from 0.2 to 1.5 percent, by weight of the hide stock.
7. A method as in claim 1 wherein said proteolytic enzyme is present in an amount from 0.01 to 3 percent, by weight of the hide stock, and has an enzymatic activity from 500 to 10,000 Lohlein-Volhard units per gram.
8. A method for the wet degreasing of hide stock consisting of raw hides or skins, pelts, or wet blues under the conditions of enzymatic bating, which method involves enzymatically bating said hide stock with a bate consisting essentially of deliming agents, a proteolytic enzyme in combination with an amylase, and a combination of synthetic surface active substances including a nonionic emulsifier together with an anionic emulsifier.
9. A method as in claim 8 wherein said enzymatic bating is carried out in the acid pH range.
10. A method as in claim 8 wherein said emulsifiers have an HLB value, with respect to their oil-in-water emulsifying activity, from 8 to 18.
11. A method as in claim 10 wherein said HLB value is from 9 to 15.
12. A method as in claim 8 wherein said combination of synthetic surface active substances is present in an amount from 0.1 to 5 percent, by weight of the hide stock.
13. A method as in claim 8 wherein said combination of surface active substances is present in an amount from 0.2 to 1.5 percent, by weight of the hide stock.
14. A method as in claim 8 wherein said proteolytic enzyme is present in an amount from 0.01 to 3 percent, by weight of the hide stock, and has an enzymatic activity from 500 to 10,000 Loehlein-Volhard units per gram.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833312840 DE3312840A1 (en) | 1983-04-09 | 1983-04-09 | Method for the wet degreasing of hide material |
| DE3312840 | 1983-04-09 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07088467 Continuation | 1987-08-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4968621A true US4968621A (en) | 1990-11-06 |
Family
ID=6195885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/391,638 Expired - Lifetime US4968621A (en) | 1983-04-09 | 1989-08-07 | Method for the wet degreasing of hide and skin stock |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4968621A (en) |
| JP (1) | JPS59197500A (en) |
| AU (1) | AU558447B2 (en) |
| DE (1) | DE3312840A1 (en) |
| FR (1) | FR2543974A1 (en) |
| HU (1) | HU195255B (en) |
| IT (1) | IT1180048B (en) |
| NZ (1) | NZ207769A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089414A (en) * | 1989-07-11 | 1992-02-18 | Rohm Gmbh | Enzymatic soaking method |
| US5891083A (en) * | 1997-04-22 | 1999-04-06 | Capella; Rafael F. | Suction lipolysis |
| US5931970A (en) * | 1995-05-12 | 1999-08-03 | Stockhausen Gmbh & Co. Kg | Process for treating leathers with surfactants to improve water repellency |
| US20030061666A1 (en) * | 2001-05-01 | 2003-04-03 | Blc Leather Technology Centre Limited Leather Trade House | Leather processing |
| US20060143833A1 (en) * | 2001-07-20 | 2006-07-06 | Basf Aktiengesellschaft | Leather degreasing agent |
| US20060293207A1 (en) * | 2005-06-28 | 2006-12-28 | Shawn Porter | Tobacco ash hair color stain remover |
| EP2510809A2 (en) | 2011-04-15 | 2012-10-17 | Select Pet Products Europe | Degradable animal chew toy and method of making same |
| US8613261B2 (en) | 2010-11-22 | 2013-12-24 | Salix Animal Health, Llc | Method of making a degradable animal chew toy |
| CN114953626A (en) * | 2022-06-07 | 2022-08-30 | 顾勇杰 | Collagen fiber composite base material and manufacturing process and manufacturing production line thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3704465C2 (en) * | 1987-02-13 | 1995-11-02 | Roehm Gmbh | Liquid formulations of enzymes |
| DE4212568A1 (en) * | 1992-04-15 | 1993-10-21 | Roehm Gmbh | Flesh removal on fresh skins for leather prodn. - comprises applying proteolytic enzyme with strong elastolcytic activity at pH 5-10 and 5-30 deg. C prior to lifting |
| RU2322510C1 (en) | 2003-12-17 | 2008-04-20 | Акцо Нобель Н.В. | Method of treatment of animals' skins |
| JP5250382B2 (en) * | 2008-10-24 | 2013-07-31 | 省二 奥海 | Tannery pre-treatment method and tannery method |
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| AU431017A (en) * | 1916-05-17 | 1917-09-15 | Arthur Henry Short | An improved combined electric lampholder and lamplock |
| US2121823A (en) * | 1934-06-29 | 1938-06-28 | Ici Ltd | Manufacture of sulphonium compounds |
| US2871162A (en) * | 1953-02-26 | 1959-01-27 | Burton Donald | Process for the treatment of hides and skins with mucolytic enzymes |
| US2965678A (en) * | 1951-12-28 | 1960-12-20 | Gen Aniline & Film Corp | Polyoxyethylene ethers of branched chain alcohols |
| US3076749A (en) * | 1959-06-24 | 1963-02-05 | Roehm & Haas Gmbh | Method of unhairing skins and hides |
| US3203868A (en) * | 1962-04-06 | 1965-08-31 | Roehm & Haas Gmbh | Method for preparing tannable depilated hides |
| US3558430A (en) * | 1967-03-03 | 1971-01-26 | Roehm & Haas Gmbh | Process for the loosening of dead hairs in fur pelts |
| US3986926A (en) * | 1973-01-13 | 1976-10-19 | Rohm Gmbh | Method for preparing tannable pelts from animal skins and hides |
| US4260686A (en) * | 1978-08-23 | 1981-04-07 | Henkel Kommanditgesellschaft Auf Aktien | Process for the enzymatic softening of furs |
| US4273876A (en) * | 1978-12-27 | 1981-06-16 | Rohm Gmbh | Enzymatic bating method |
| US4314801A (en) * | 1979-11-03 | 1982-02-09 | Rohm Gmbh | Soaking method |
| US4344762A (en) * | 1979-11-03 | 1982-08-17 | Rohm Gmbh | Soaking method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE888741C (en) * | 1943-09-14 | 1953-09-03 | Roehm & Haas G M B H | Process for pickling dehaired skins and pelts using proteolytic enzymes |
| DE1022350B (en) * | 1952-07-15 | 1958-01-09 | Roehm & Haas Gmbh | Give way to furs and skins |
| DE927464C (en) * | 1953-09-04 | 1955-05-09 | Roehm & Haas G M B H | Process for the production of tanned bare |
| DE974813C (en) * | 1954-12-24 | 1961-05-04 | Roehm & Haas G M B H | Process for pickling animal skin |
| DE975095C (en) * | 1955-01-01 | 1961-08-10 | Roehm & Haas G M B H | Method for pickling animal bare with pancreatic enzyme preparations |
| DE1120066B (en) * | 1955-03-23 | 1961-12-21 | Roehm & Haas Gmbh | Process for pickling animal skin |
| JPS49118801A (en) * | 1973-03-26 | 1974-11-13 | ||
| DE2522902C3 (en) * | 1975-05-23 | 1979-12-13 | Chemische Fabrik Stockhausen & Cie, 4150 Krefeld | Process for the simultaneous softening, cleaning and degreasing of raw fumes |
-
1983
- 1983-04-09 DE DE19833312840 patent/DE3312840A1/en not_active Withdrawn
-
1984
- 1984-04-04 JP JP59066032A patent/JPS59197500A/en active Granted
- 1984-04-06 HU HU841354A patent/HU195255B/en not_active IP Right Cessation
- 1984-04-06 NZ NZ207769A patent/NZ207769A/en unknown
- 1984-04-06 IT IT67357/84A patent/IT1180048B/en active
- 1984-04-09 FR FR8405571A patent/FR2543974A1/en active Pending
- 1984-04-09 AU AU26637/84A patent/AU558447B2/en not_active Ceased
-
1989
- 1989-08-07 US US07/391,638 patent/US4968621A/en not_active Expired - Lifetime
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089414A (en) * | 1989-07-11 | 1992-02-18 | Rohm Gmbh | Enzymatic soaking method |
| US5931970A (en) * | 1995-05-12 | 1999-08-03 | Stockhausen Gmbh & Co. Kg | Process for treating leathers with surfactants to improve water repellency |
| US5891083A (en) * | 1997-04-22 | 1999-04-06 | Capella; Rafael F. | Suction lipolysis |
| US20030061666A1 (en) * | 2001-05-01 | 2003-04-03 | Blc Leather Technology Centre Limited Leather Trade House | Leather processing |
| US20100263134A1 (en) * | 2001-05-01 | 2010-10-21 | Blc Leather Technology Centre Limited Leather Trade House | Leather processing |
| US20060143833A1 (en) * | 2001-07-20 | 2006-07-06 | Basf Aktiengesellschaft | Leather degreasing agent |
| US20060293207A1 (en) * | 2005-06-28 | 2006-12-28 | Shawn Porter | Tobacco ash hair color stain remover |
| US8613261B2 (en) | 2010-11-22 | 2013-12-24 | Salix Animal Health, Llc | Method of making a degradable animal chew toy |
| US9265233B2 (en) | 2010-11-22 | 2016-02-23 | Spectrum Brands, Inc. | Degradable animal chew toy |
| EP2510809A2 (en) | 2011-04-15 | 2012-10-17 | Select Pet Products Europe | Degradable animal chew toy and method of making same |
| CN114953626A (en) * | 2022-06-07 | 2022-08-30 | 顾勇杰 | Collagen fiber composite base material and manufacturing process and manufacturing production line thereof |
| CN114953626B (en) * | 2022-06-07 | 2024-05-03 | 顾勇杰 | Collagen fiber composite substrate and manufacturing process and manufacturing production line thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU558447B2 (en) | 1987-01-29 |
| HUT41847A (en) | 1987-05-28 |
| HU195255B (en) | 1988-04-28 |
| FR2543974A1 (en) | 1984-10-12 |
| JPH0464360B2 (en) | 1992-10-14 |
| DE3312840A1 (en) | 1984-10-11 |
| IT8467357A1 (en) | 1985-10-06 |
| NZ207769A (en) | 1987-04-30 |
| AU2663784A (en) | 1984-10-11 |
| IT1180048B (en) | 1987-09-23 |
| IT8467357A0 (en) | 1984-04-06 |
| JPS59197500A (en) | 1984-11-09 |
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